Process for dyeing and coloring in the mass with perlyene derivatives



2,998,402 Patented Aug. 29, 1961 2,998,402 PROCESS FOR DYEING ANDCOLORING IN THE MASS WITH PERLYENE DERIVATIVES Georg Geiger and KarlUlrich Steiner, Binningen, Switzerland, assignors to Sandoz A.G., Basel,Switzerland, 21 Swiss firm No Drawing. Filed Oct. 20,1958, Ser. No.768,054 Claims priority, application Switzerland Oct. 29, '1957 11Claims. (Cl. 260-37) It has been found that the halogenated orunhalogenated condensation products of a halogenated or unhalogenatedperylene-3,4,9, l-tetracarboxylic acid with orthoorperiarylene-diamines, which latter may contain further substituents, arehighly suitable upon conversion into finely divided form for thecoloring of lacquer media, printing inks and plastics, and for thedyeing of regenerated cellulose, cellulose ether, cellulose ester andsynthetic polymer fibers in the mass.

Lacquers, plastics and the above named classes of manufactured fiberscolored or dyed with these products possess good light fastness and goodwet fastness properties. The dyestuffs show other interestingproperties, e.g., good :fastness to migration in polyvinyl chloride,provided they contain no more than two chlorine atoms in the molecule,good resistance to top coating finishes in lacquers, good fastness tooverprinting in printing inks, high resistance to heat in all plastics,especially in polyamides (e.g. nylon, Perlon, Rilsan (registered trademarks)) and polyesters (egj Diolen, Dacron, Terylene (registered trademarks)) in the melted state, and good fastness to chlorine bleaching andperoxide bleaching in spun-dyed acetate, polyamide and polyester fibers.

The dyestuffs have the general formulae:

wherein R stands for the radical of an orthoor peri-arylene such asortho-phenylene, 1,2- or 1,8-naphthylene,

R for hydrogen, halogen, alkyl or alkoxy,

R for hydrogen or halogen, and

R for hydrogen or halogen.

These perylene derivatives are obtained by heatingperylene-3,4,9,lO-tetracarboxylic anhydride or its halogen derivativeswith the corresponding diamines at temperatures of 150-250 C., ifdesired in inert solvents such as nitrobenzene, trichlorobenzene, or inalcohols of high boiling point (benzyl alcohol, lauryl alcohol), or inquinoline, etc., and if desired with the addition of dehydrating agentssuch as ZnCl or similar products, or insolvents of low boiling pointsuch as chlorobenzenes or water under pressure. Initially only one ofthe two amino groups reacts and the di-imine is formed then upon heatingfor a longer period or at a higher temperature the pyrimidine or theirnidazole rings are closed. The condensation product thus formed can besubsequently halogenated if necessary, e.g. in concentrated sulfuricacid or chlorosulfonic acid in presence of a halogen carrier (iodine) atroom temperature or a moderately high temperature.

It is preferable to bring the dyestuffs into a fine form before use, forexample by reprecipitation from sulfuric acid, e.g. from thechlorination solution, or by grinding in presence of grindingassistants.

In the following table are listed some perylene derivatives which aresuitable for dyeing and coloring in the mass. They are characterized bythe starting materials used (columns I and H) and by the shade they givein polyvinyl chloride (column HI).

Produced by the process of German Patent 441,587. (9) After condensation2 chlorine atoms are introduced into the dyestufl molecule.

(10) After condensation 1 chlorine atom is introduced into the dye stufimolecule.

(11) After condensation 1 bromine atom is introduced into the dyestufimolecule.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 0.1 part of the pigment dyestuif No. 1 of the table is Wettedwith 1 part of dioctyl phthalate and pasted with a spatula. parts of apreviously prepared mixture of 0.05 part of the pigment dyestuif No. ofthe table and 100 parts of polystyrene molding powder are placed in aclosed vessel and vigorously shaken for minutes. The mixture iscompounded on a roller mill, one roller of which is heated to 120 andthe other to 150, until the dyestuif is uniformly dispersed. The coloredmass is allowed to cool and the particle size reduced to about v24 mm.by grinding in a suitable mill. It is then fed into an injection moldingmachine operating at 160240 for the production of molded articles of anydesired shape. They are of reddish blue color and show good fastness tolight.

Example 3 In a closed vessel 0.05 part of the pigment dyestuif No. 3 ofthe table and 100 parts of polyethylene molding powder are vigorouslyagitated for 10 minutes, The mixture is worked up on a roller mill, oneroller of which is heated to 150 and the other to 120, until thedyestutf is homogeneously dispersed. After cooling, the mass is groundin a suitable mill to a particle size of about 2-4 mm. It is then moldedinto the desired articles on suitable equipment such as an extrusion orinjection molder. The molded goods are of a violet color and have goodcolor fastness properties.

Example 4 30 parts of pigment dyestuff No. 1 of the table are mixed with5000 parts of nylon 66 and melted in the normal way, i.e. in a nitrogenatmosphere at about 285 The thick liquid mass is spun to give a filamentof violet shade with good fastness to light and wet treatments. It canbe orientated and/or crimped and shrinkproofed by suitable heattreatments.

Example 5 Example 6 A mixture of 100 parts of secondary celluloseacetate of 54-55% acetic acid content, 400 parts of acetone and 1 partof the pigment dyestuff No.6 of the table are ground in a ball milluntil the film formed by pouring a sample onto a glass plate is found bymicroscopic examination to contain only a negligible proportion ofparticles larger than la. The mass is then spun into a reddish bluefilament which is outstandingly fast to light and withstands all thenormal textile processes without loss of color strength.

Example 7 1 part of the pigment dyestuff No, 2 of the table iscompounded in suitable equipment, for example a roller mill, with 4parts of water and if desired an addition of a dispersing agent such assodium dinaphthylmethanedisulfonate. When the pigment paste ishomogeneous it is stirred into 1170 parts of a viscose solution of 8.5%u-cellulose content. The colored viscose is spun in the normal way togive a violet filament of very good light and wet fastness.

The dyestufi' can be brought into a finely divided form byreprecipitation from sulfuric acid or by grinding. It is washed toneutralize it or to eliminate the grinding assistants, as the case maybe, and can then be pasted on the roller mill without intermediatedrying.

Example 8 In a three-roller mill 1 part of the pigment dyestufi No. 4 ofthe table and 5 parts of aluminum hydroxide are pasted with sufiicientboiled linseed oil to form a printing ink of the desired consistency.The ink gives violet colored prints on paper which have good fastness tolight and overprinting.

Example 9 100 parts of a commercial nitrocellulose lacquer medium arecolored with 2 parts of pigment dyestuli No. 8 of the table. The lacquercan be applied by spraying or dipping methods to give reddish violetcoatings of excellent fastness to light and top finishes.

Example 10 1 part of the pigment dyestufi. No. l of the table isdissolved in 10-20 parts of sulfuric acid of -100% concentration, ifnecessary with heating, and subsequently precipitated in parts of waterwith vigorous stirring. The suspension so formed is filtered ofi, washedneutral with water and dried. The dyestuif is thereby obtained in a fineform which in many cases can be dispersed better and quicker in themedium to be colored.

Example 1] 1 part of the pigment dyestuif No. 5 of the table is groundin a ball mill with 10 parts of a solid grinding assistant, e.g. commonsalt, potassium chloride, calcium chloride or carbonate, urea, phthalicacid or similar products, until the crystals of the raw dyestuff havelargely disappeared. The mass is stirred into water with the addition ofthe necessary amount of hydrochloric acid or caustic soda respectivelyif an acid-soluble or alkali-soluble grinding assistant has been used.After filtration and washing to eliminate the grinding assistant, thedyestuif is obtained in a fine form which in many cases is dispersed inthe medium more rapidly and better than otherwise.

Example 12 0.1 part of the pigment dyestufi No. 7 of the table is wettedwith 1 part of dioctyl phthalate and pasted with a spatula. The paste ismixed with a previously prepared mixture of 60 parts of polyvinylchloride, 40 parts of dioctyl phthalate and the commonly usedstabilizers. The mixture is gelatinized on a roller mill in 10 minutesat 150 and then machine pressed between polished plates heated to about140. The plastic sheet or skin thus produced is of a reddish blue colorwhich has excellent fastness to light and migration.

Example 13 30 parts of the pigment dyestuff No. 9 of the table are mixedwith 5000 parts of Rilsan (registered trademark) and melted by thenormal method in a nitrogen atmosphere at a temperature of about 230.The thick liquid melt is spun into filament of reddish violet shade. Ithas good fastness to light, chlorine bleaching, peroxide bleaching andwet treatments, and can be orientated and/or crimped and shrinkproofedif desired.

Equally good results are obtained with dyestuffs Nos.

Having thus disclosed the invention what we claim is: 1. In a processfor the dyeing of fibers of synthetic polyamides and polyesters in themass, the improvement and 2. A process according to claim 1 wherein thedyestuif is of the formula 6 y 3. A process according to claim 1 whereinthe dyestufi is of the formula o o 2 4. A process according to claim 1wherein the dyestufi is of the formula 5. A process according to claim 1wherein the dyestulf is of the formula 6. A process according to claim 1which consists in the use of the dyestufl of the formula 7. A processfor dyeing synthetic polyamides and polyesters in the mass with adyestufi as defined in claim 1, wherein the dyestufi is preliminarilyintimately admixed with the material to be dyed, and then homogenizationof the mixture completed at about the melting temperature of saidmaterial.

8. The process described in claim 1, wherein the fibers are of nylon.

9. Synthetic polyamide fibers, dyed in the mass with the dyestutfdefined in claim 1.

10. Synthetic polyester fibers, dyed in the mass with the dyestuifdefined in claim 1.

11. Nylon fibers dyed in the mass with the dyestuif claimed in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS Waterset a1 Oct. 16, 1951 UNITED STATES PATENT OFFICE CERTIFICATION OFCORRECTION PatentNo. 2,998,402 August 29 1961 Georg Geiger et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2,, line 15, for insolvents" read in solvents column 5 linesl8'to. 20 the lower part of the first formula should appear as shownhelowinstead of as in the patent:

same column 5, lines 38 to 4O the lower part of the second formulashould appear as shown below instead of as in the patent: I

same column line 46 for "Each" read each Signed and sealed this 24th dayof April 1962.,

(SEAT) Attest:

ESTON 1G} JOHNSON DAVID L. LADD Commissioner of Patents AttestingOfficer

1. IN A PROCESS FOR THE DYEING OF FIBERS OF SYNTHETIC POLYAMIDES ANDPOLYESTERS IN THE MASS, THE IMPROVEMENT WHICH CONSISTS IN CARRYING OUTTHE DYEING IN THE MASS WITH A DYESTUFF OF THE FORMULA ULAE